US4551318A - Stabilized solutions of hydroxylamine or its salts in water or alcohols, and their preparation - Google Patents
Stabilized solutions of hydroxylamine or its salts in water or alcohols, and their preparation Download PDFInfo
- Publication number
- US4551318A US4551318A US06/685,257 US68525784A US4551318A US 4551318 A US4551318 A US 4551318A US 68525784 A US68525784 A US 68525784A US 4551318 A US4551318 A US 4551318A
- Authority
- US
- United States
- Prior art keywords
- hydroxylamine
- stabilized
- solution
- salts
- formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/082—Compounds containing nitrogen and non-metals and optionally metals
- C01B21/14—Hydroxylamine; Salts thereof
- C01B21/149—Stabilisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C53/00—Saturated compounds having only one carboxyl group bound to an acyclic carbon atom or hydrogen
- C07C53/08—Acetic acid
- C07C53/10—Salts thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C53/00—Saturated compounds having only one carboxyl group bound to an acyclic carbon atom or hydrogen
- C07C53/122—Propionic acid
Definitions
- the present invention furthermore relates to a process for the preparation of stabilized solutions of hydroxylamine or its salt by the addition of stabilizers, wherein the molecular oxygen dissolved in the solution to be stabilized is removed from this solution by treatment with nitrogen which is free of molecular oxygen, and an anthocyan of the formula I is then added.
- solutions of hydroxylamine or its salts which have been stabilized according to the invention have the advantage that they are stable over a longer period than prior art solutions, and in particular the decomposition of free hydroxylamine is reduced to a minimum.
- a solution of hydroxylamine or one of its salts in water or an alcohol eg. a C 1 -C 4 -alkanol is used as the starting material.
- suitable salts of hydroxylamine are those with a strong mineral acid, such as sulfuric acid, nitric acid or hydrochloric acid, or those with fatty acids, eg. acetic acid or propionic acid.
- hydroxylamine is preferably in the form of a solution in water or an alcohol, whereas its salts are preferably present as aqueous solutions.
- the content of hydroxylamine or its salts is, as a rule, from 10 to 70% by weight, and the hydroxylamine solutions used generally have a pH of from 8 to 11. Particularly preferably, aqueous hydroxylamine solutions are used as starting materials.
- the stabilizers used are anthocyans of the formula ##STR3## where R 1 , R 2 , R 3 and R 4 are each hydrogen, hydroxyl or C 1 -C 4 -alkoxy and X is an anion of a strong mineral acid. X is preferably a chloride or sulfate anion. In particularly preferred anthocyans of the formula I, R 1 , R 2 , R 3 and R 4 are each hydrogen, hydroxyl or methoxy and X is a chloride anion.
- the anthocyans can also be present in the form of glycosides. Suitable anthocyans are described in, for example, Angew. Chem. 68 (1956), 110 and 111, useful compounds being apigenin, pelargonidin, cyanidin, delphinidin, peonidin, petunidin and malvidin.
- the anthocyans of the formula I are used in amounts of from 0.005 to 1, in particular from 0.01 to 0.1, % by weight, based on the solution to be stabilized.
- polyhydroxybenzenes in particular pyrogallol, in addition has also proven useful, the polyhydroxybenzenes advantageously being added in amounts of from 0.005 to 0.1% by weight, based on the solution to be stabilized. It is noteworthy that the combined use of anthocyans of the formula I and polyhydroxybenzenes results in a synergistic effect.
- Stabilized solutions of hydroxylamine or its salts in water or in alcohols are prepared, according to the invention, by a method in which the molecular oxygen dissolved in the solution to be stabilized is first displaced from this solution by treatment with nitrogen which is free of molecular oxygen. This is achieved by, for example, passing oxygen-free nitrogen through the solution to be stabilized, for example for from 5 to 10 minutes.
- the nitrogen used for this purpose advantageously contains less than 2 ppm of molecular oxygen.
- Anthocyans of the formula I and, if required, hydroxybenzenes are then added, and are dissolved in the said solution, the temperature advantageously being kept at from 5° to 40° C. during this procedure. It is also possible to add the stabilizers in the form of solutions to the solution to be stabilized.
- the solution to be stabilized is prevented from becoming contaminated with heavy metals, in particular copper or noble metals, since these catalyze decomposition of hydroxylamine. It is also advantageous to exclude high-energy radiation by means of suitably colored glass containers, and to store the stabilized solutions at ⁇ 40° C., for example at from 5° to 20° C.
- Stabilized solutions of hydroxylamine or its salts are useful for the preparation of oximes.
- aqueous solution of hydroxylamine is flushed with oxygen-free nitrogen at 20° C. for 10 minutes, after which the stabilizer is added.
- concentration of hydroxylamine, the type and amount of the stabilizer added and the results achieved as a function of time and temperature are shown in the Table below.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Medicinal Preparation (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Pyrane Compounds (AREA)
Abstract
Description
TABLE ______________________________________ Stabilizer °C. ______________________________________ 50 ppm of 5 0 743 1198 Hours cyanidin 110.88 110.73 110.50 g/l of NH.sub.2 OH 50 ppm of 20 0 404 1195 Hours cyanidin 110.25 109.65 109.39 g/l of NH.sub.2 OH 50 ppm of 40 0 359 1194 Hours cyanidin 110.25 109.70 108.67 g/l of NH.sub.2 OH ______________________________________
Claims (5)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE3347260 | 1983-12-28 | ||
DE3347260A DE3347260A1 (en) | 1983-12-28 | 1983-12-28 | STABILIZED SOLUTIONS OF HYDROXYLAMINE OR ITS SALT IN WATER OR ALCOHOLS AND THEIR PRODUCTION |
Publications (1)
Publication Number | Publication Date |
---|---|
US4551318A true US4551318A (en) | 1985-11-05 |
Family
ID=6218268
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US06/685,257 Expired - Lifetime US4551318A (en) | 1983-12-28 | 1984-12-24 | Stabilized solutions of hydroxylamine or its salts in water or alcohols, and their preparation |
Country Status (5)
Country | Link |
---|---|
US (1) | US4551318A (en) |
EP (1) | EP0147742B1 (en) |
JP (1) | JPS60155512A (en) |
DE (2) | DE3347260A1 (en) |
DK (1) | DK162834C (en) |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1998049099A1 (en) * | 1997-04-30 | 1998-11-05 | Alliedsignal Inc. | Stabilized hydroxylamine solutions |
US20030026751A1 (en) * | 2000-02-22 | 2003-02-06 | Markus Weber | Stabilizing agent for hydroxylamine solutions |
US20090112024A1 (en) * | 2007-10-29 | 2009-04-30 | Wai Mun Lee | Stabilization of hydroxylamine containing solutions and method for their preparation |
US20090130849A1 (en) * | 2007-10-29 | 2009-05-21 | Wai Mun Lee | Chemical mechanical polishing and wafer cleaning composition comprising amidoxime compounds and associated method for use |
US20090137191A1 (en) * | 2007-10-29 | 2009-05-28 | Wai Mun Lee | Copper cmp polishing pad cleaning composition comprising of amidoxime compounds |
US20100043823A1 (en) * | 2007-10-29 | 2010-02-25 | Wai Mun Lee | Methods of cleaning semiconductor devices at the back end of line using amidoxime comositions |
US20100105595A1 (en) * | 2008-10-29 | 2010-04-29 | Wai Mun Lee | Composition comprising chelating agents containing amidoxime compounds |
US20100105594A1 (en) * | 2008-10-29 | 2010-04-29 | Wai Mun Lee | Process of purification of amidoxime containing cleaning solutions and their use |
US20110065622A1 (en) * | 2007-10-29 | 2011-03-17 | Wai Mun Lee | Novel nitrile and amidoxime compounds and methods of preparation for semiconductor processing |
US8802609B2 (en) | 2007-10-29 | 2014-08-12 | Ekc Technology Inc | Nitrile and amidoxime compounds and methods of preparation for semiconductor processing |
Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3145082A (en) * | 1959-12-07 | 1964-08-18 | Dow Chemical Co | Stabilized hydroxylamine and its method of preparation |
US3480392A (en) * | 1967-08-24 | 1969-11-25 | Sinclair Research Inc | Hydroxylamine solutions stabilized with a hydroxamic acid and method for their preparation |
US3480391A (en) * | 1967-08-24 | 1969-11-25 | Sinclair Research Inc | Hydroxylamine solutions stabilized with an amide oxime and method for their preparation |
US3544270A (en) * | 1968-08-13 | 1970-12-01 | Sinclair Oil Corp | Aqueous hydroxylamine solutions stabilized with hydroxyurea or hydroxythiourea derivatives |
NL7703020A (en) * | 1977-03-19 | 1978-09-21 | Stamicarbon | Stabilisation of hydroxylamine salt soln. contg. noble metal catalyst - by treating the catalyst with an opt. substd. unsaturated hydrocarbon |
JPS57100908A (en) * | 1980-12-16 | 1982-06-23 | Nisshin Kako Kk | Stabilization of hydroxylamine or solution containing it by addition of 8 hydroxyquinoline |
JPS5869843A (en) * | 1981-10-20 | 1983-04-26 | Nisshin Kako Kk | Stabilizer for hydroxylamine |
JPS5869844A (en) * | 1981-10-20 | 1983-04-26 | Nisshin Kako Kk | Stabilizer for hydroxylamine |
JPS5869841A (en) * | 1981-10-20 | 1983-04-26 | Nisshin Kako Kk | Stabilizer for hydroxylamine |
JPS5969842A (en) * | 1982-10-15 | 1984-04-20 | Fujitsu Ltd | Method for controlling command of computer system |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS595574B2 (en) * | 1981-10-20 | 1984-02-06 | 日進化工株式会社 | Hydroxylamine stabilizer |
-
1983
- 1983-12-28 DE DE3347260A patent/DE3347260A1/en not_active Withdrawn
-
1984
- 1984-12-14 DE DE8484115403T patent/DE3464578D1/en not_active Expired
- 1984-12-14 EP EP84115403A patent/EP0147742B1/en not_active Expired
- 1984-12-21 DK DK619684A patent/DK162834C/en not_active IP Right Cessation
- 1984-12-24 US US06/685,257 patent/US4551318A/en not_active Expired - Lifetime
- 1984-12-24 JP JP59271089A patent/JPS60155512A/en active Pending
Patent Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3145082A (en) * | 1959-12-07 | 1964-08-18 | Dow Chemical Co | Stabilized hydroxylamine and its method of preparation |
US3480392A (en) * | 1967-08-24 | 1969-11-25 | Sinclair Research Inc | Hydroxylamine solutions stabilized with a hydroxamic acid and method for their preparation |
US3480391A (en) * | 1967-08-24 | 1969-11-25 | Sinclair Research Inc | Hydroxylamine solutions stabilized with an amide oxime and method for their preparation |
US3544270A (en) * | 1968-08-13 | 1970-12-01 | Sinclair Oil Corp | Aqueous hydroxylamine solutions stabilized with hydroxyurea or hydroxythiourea derivatives |
NL7703020A (en) * | 1977-03-19 | 1978-09-21 | Stamicarbon | Stabilisation of hydroxylamine salt soln. contg. noble metal catalyst - by treating the catalyst with an opt. substd. unsaturated hydrocarbon |
JPS57100908A (en) * | 1980-12-16 | 1982-06-23 | Nisshin Kako Kk | Stabilization of hydroxylamine or solution containing it by addition of 8 hydroxyquinoline |
JPS5869843A (en) * | 1981-10-20 | 1983-04-26 | Nisshin Kako Kk | Stabilizer for hydroxylamine |
JPS5869844A (en) * | 1981-10-20 | 1983-04-26 | Nisshin Kako Kk | Stabilizer for hydroxylamine |
JPS5869841A (en) * | 1981-10-20 | 1983-04-26 | Nisshin Kako Kk | Stabilizer for hydroxylamine |
JPS5969842A (en) * | 1982-10-15 | 1984-04-20 | Fujitsu Ltd | Method for controlling command of computer system |
Cited By (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1998049099A1 (en) * | 1997-04-30 | 1998-11-05 | Alliedsignal Inc. | Stabilized hydroxylamine solutions |
US5906805A (en) * | 1997-04-30 | 1999-05-25 | Alliedsignal Inc. | Stabilized hydroxylamine solutions |
CN1120128C (en) * | 1997-04-30 | 2003-09-03 | Basf公司 | Stabilized hydroxylamine solutions |
US20030026751A1 (en) * | 2000-02-22 | 2003-02-06 | Markus Weber | Stabilizing agent for hydroxylamine solutions |
US6758990B2 (en) | 2000-02-22 | 2004-07-06 | Basf Aktiengesellschaft | Stabilizing agent for hydroxylamine solutions |
US20090130849A1 (en) * | 2007-10-29 | 2009-05-21 | Wai Mun Lee | Chemical mechanical polishing and wafer cleaning composition comprising amidoxime compounds and associated method for use |
US20090112024A1 (en) * | 2007-10-29 | 2009-04-30 | Wai Mun Lee | Stabilization of hydroxylamine containing solutions and method for their preparation |
US20090137191A1 (en) * | 2007-10-29 | 2009-05-28 | Wai Mun Lee | Copper cmp polishing pad cleaning composition comprising of amidoxime compounds |
US20100043823A1 (en) * | 2007-10-29 | 2010-02-25 | Wai Mun Lee | Methods of cleaning semiconductor devices at the back end of line using amidoxime comositions |
US20110065622A1 (en) * | 2007-10-29 | 2011-03-17 | Wai Mun Lee | Novel nitrile and amidoxime compounds and methods of preparation for semiconductor processing |
US8062429B2 (en) | 2007-10-29 | 2011-11-22 | Ekc Technology, Inc. | Methods of cleaning semiconductor devices at the back end of line using amidoxime compositions |
US8802609B2 (en) | 2007-10-29 | 2014-08-12 | Ekc Technology Inc | Nitrile and amidoxime compounds and methods of preparation for semiconductor processing |
US20100105595A1 (en) * | 2008-10-29 | 2010-04-29 | Wai Mun Lee | Composition comprising chelating agents containing amidoxime compounds |
US20100105594A1 (en) * | 2008-10-29 | 2010-04-29 | Wai Mun Lee | Process of purification of amidoxime containing cleaning solutions and their use |
US7838483B2 (en) | 2008-10-29 | 2010-11-23 | Ekc Technology, Inc. | Process of purification of amidoxime containing cleaning solutions and their use |
Also Published As
Publication number | Publication date |
---|---|
EP0147742B1 (en) | 1987-07-08 |
DK619684A (en) | 1985-06-29 |
DK162834C (en) | 1992-05-04 |
JPS60155512A (en) | 1985-08-15 |
DE3347260A1 (en) | 1985-07-11 |
DK162834B (en) | 1991-12-16 |
EP0147742A2 (en) | 1985-07-10 |
DE3464578D1 (en) | 1987-08-13 |
EP0147742A3 (en) | 1986-03-12 |
DK619684D0 (en) | 1984-12-21 |
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Owner name: BASF AKTIENGESELLSCHAFT, 6700 LUDWIGSHAFEN, RHEINL Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNORS:GROSSKINSKY, OTTO-ALFRED;FROMMER, ELMAR;RITZ, JOSEF;AND OTHERS;REEL/FRAME:004427/0513 Effective date: 19841218 |
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